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Special Thanks: The original author of this paper, Jean-Jacques Wolff, was born on April 23, 1930. He first studied Chemistry and then Bio-technology. He worked in the sugar and sweetener field of the food industry prior to joining a growing producer of ion exchange resins, Duolite, in the early 1960s. There he progressed quickly to become Technical Manager. Following the acquisition of Duolite by Rohm and Haas in June 1984, he decided to reinforce the technical team of a new fast-growing manufacturer of ion exchange and adsorbent resins called Purolite International. There he brought his deep expertise in the Nuclear Industry, mainly to lectricit de France. Jean-Jacques Wolff was well known and appreciated by his clients all over the world, especially in Asia. He was an excellent open minded colleague and during his life developed many new purification processes. Jean-Jacques Wolff was married and had two sons. He passed away on 25th November 1992.
Table of Contents
INTRODUCTION SECTION 1: NUCLEAR POWER GENERATION A. Nuclear Fission B. Controlling the reaction C. Nuclear Industry Water Quality Guidelines D. System Contaminants SECTION 2: TYPES OF REACTORS & WATER TREATMENT CIRCUITS A. Graphite-Gas Reactor (AGR) Graphite-Gas Reactor Treatment Circuits 1. Makeup Water 2. Condensate Polishing 3. Turbo-blowers 4. Spent Fuel Ponds B. Pressurized Water Reactors (PWR) PWR Primary Circuit Treatment 1. Reactor Coolant Purification a. Outage Clean-up Beds b. pH Control (CVCS) c. Outage Activity 2. Deboration 3. Spent Fuel Ponds (SFP) 4. Radwaste Effluent Treatment PWR Secondary Circuit Treatment 5. Makeup water Treatment 6. Condensate Polishing 7. Steam Generator Blowdown Treatment C. Boiling Water Reactors (BWR) BWR Circuit Treatment 1. Makeup water Treatment 2. Condensate Polishing 3. Reactor Coolant Purification 4. Spent Fuel Pool Treatment 5. Radwaste Treatment D. Fast Breeder Reactor (LMFBR) SECTION 3: NUCLEAR ION EXCHANGE RESIN 1. Nuclear Quality Resin 2. Operating Capacity 3. Decontamination Capacity SECTION 4: REFERENCES Page 3 Page 4
Page 8 Page 8
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1.
INTRODUCTION
Nuclear power plants are currently operated in 31 countries with 15 more countries currently planning the construction of their first nuclear power plants. Nuclear power generation will continue to grow as a strategic option due to the increasing cost of fossil fuel based energy and the pressure to reduce greenhouse gases. Ion exchange resins in both bead and powder form are used extensively in all types of nuclear power plants throughout the world. Ion exchange systems are the most cost effective and in some cases the only way to produce water with the quality required for proper plant operation. Ion exchange plays a vital role in the elimination of soluble chemical components that contribute to corrosion as well as removing corrosion products and radioactive isotopes from the different coolant circuits. The objective of controlling these chemistries is to protect the nuclear generating systems from corrosion, extend the system life and maintain a safe working environment in and around the plant. The purpose of this paper is to review the different types of nuclear reactors that are in use today, and explain in some detail the important role that ion exchange systems (and ion exchange resins) play in the different nuclear applications.
Note: All Purolite products referred to in this paper are Purolite unless specifically noted.
The relationship between these processes must be precisely managed to achieve optimal control of the reactor. When a state of equilibrium is reached the reactor is said to be critical or that it has diverged. During the life of the reactor fuel, the concentration of 235U, and therefore the neutron flux rate, decreases. The accumulation of fission products causes parasitic absorption of neutrons which further decreases neutron flux. In order to compensate for these effects, control rods are progressively removed during operation or the concentration of adsorbent in the moderator is reduced. If the production of neutrons falls below the critical level that is required to produce energy, the fuel must be replaced in a refueling outage. This occurs during a scheduled shutdown in which a portion of the fuel rods are replaced and the remaining rods are rearranged. Refueling outages are typically carried out every 18 to 24 months for most reactor designs. Several reactor designs allow operators to change fuel while the facility is still generating power. Figure 1:
D. System Contaminants
During operation, sodium will concentrate in crevices and points of evaporation, resulting in high sodium alkalinity which contributes to stress corrosion cracking in steam generator tubes and on turbine components. The sodium specification for nuclear makeup water is normally <0.1 ppb (g/kg), while the level in systems is controlled at 1.0 ppb (g/kg). Silica is also of concern in steam generators. It easily complexes with metals such as aluminum and zinc to form zeolite compounds which will accumulate on heat transfer surfaces and undermine efficient heat transfer. Many nuclear plants have adopted a reactive silica limit for the makeup water of 10 ppb, which is consistent with INPO and WANO guidelines (2, 3). This concentration limit provides adequate protection, since the boiler water silica specification is 1,000 ppb, but preferably <300 ppb. Boroflex coated fuel racks used to store spent fuel in the spent fuel pool are a significant source of silica and contribute to primary coolant treatment issues particularly at start up after a refueling outage. Total chloride and sulfate ion concentrations introduced into the systems, if not from system leaks, typically come from the ion exchange resins themselves. These impurities are present as a combination of inorganic (i.e., ionic) chlorides and sulfates and organically bound chloride (OBCl) and sulfate (OBS). The latter, i.e. the organic fraction, is not detected by ion chromatography (IC) in the makeup water since it is not ionized. These compounds degrade The Wolff Paper Apr 2012
thermally or radiolytically in the system, producing chloride and sulfate ions, which potentially reduce the water pH and lead to intergranular corrosion (IGC) and stress corrosion cracking. The typical allowable level of sulfate in the steam generator is 1.50 ppb and the allowable level of chloride is <0.5 ppb. Chloride is sometimes added back into the steam generator to help control caustic buildup (NaOH) in crevices. Total Organic Carbon (TOC) or Total Organic Hetero-atoms (TOX), where X is typically chlorine, sulphur or nitrogen, come from resins as well as degradation products from chemicals used to treat the primary and secondary coolant systems. To determine concentrations of organically bound chlorine and organically bound sulphur, it is necessary to first analyze samples using IC, followed by a second IC analysis after the sample has been subjected to UV radiation. The latter result represents total chloride and total sulfate, which includes the organically bound portion of these compounds. The concentration of total organic hetero-atoms (TOX) is the sum of all the organically bound atoms.
Transport cask lowered into an unloading pool Source: World Nuclear Association
SECTION 2: TYPES OF REACTORS & TREATMENT OF CIRCUITS A. The Graphite-Gas Reactor (Figure 2)
The Graphite-Gas Reactor was one of the first types to be introduced and quickly became the main backbone for the nuclear industry in the United Kingdom. Initial designs were the Magnox and later the AGR (Advanced Gas Cooled Reactor) system. The AGR design operates at higher temperatures, which requires certain design modification to accommodate the elevated temperatures. Today, most of the Magnox designs are no longer in operation, but there are several AGR designs still in successful commercial operation. All of these operate with two reactors in a single structure, and use uranium as the fuel. In the reactor core, the fuel rods are located inside a block of graphite that acts as a moderator. The coolant is pressurized CO2, which passes through the reactor core removing heat. This heated CO2 stream is used to produce steam, which drive turbine generators that generate electricity as part of the overall power plant. Figure 2: Magnox Reactor Schematic
Todays highly regulated nuclear power plants are considered to be safe, and produce relatively low amounts of radioactive waste material. One of the primary advantages seen with the graphite-gas design is their ability to allow for the online replacement of fuel elements. However, operating difficulties make Graphite-gas reactors commercially less attractive to build and have restricted widespread use of this design.
Figure 3:
1. Makeup water
Almost all AGR units operate their own make up treatment systems. However service providers are available to support makeup requirements with service trailers. These systems commonly employ pre-filtration followed by reverse osmosis (RO) technology with a final, high-purity mixed bed polisher. Nuclear power plants that continue to own and operate their own makeup water-treatment systems will generally use standard resins that produce high-quality water but also have good regeneration efficiency. The following resins configured in the order shown can be used to demineralize the makeup water for AGR Reactors: NRW100 strong acid cation exchanger PFA100 weak base anion exchanger NRW400 strong base anion exchanger NRW3240 for polishing mixed beds The Wolff Paper Apr 2012
This combination of resins will produce water with conductivity below 0.1 S/cm and less than 10 ppb of Si02. The makeup water recommended purity is specified in Table 1. Table 1: AGR Makeup Water Specifications Component Total Dissolved Solids Total Fe and Cu Chloride O2 pH SiO2 Specification <0.1 ppm <10 ppb <5 ppb <10 ppb 9.2 to 9.5 <10 ppb
2. Condensate Polishing
Because the heat exchanger is built into the reactor and is difficult to reach, it is important to treat 100% of the condensate and eliminate corrosion byproducts and dissolved salts that could result from condenser leaks and makeup water. Morpholine and other special amines, along with ammonia, are used to adjust water pH to the target range of 9.2 to 9.5 to minimize corrosion. Since the system contains a small quantity of makeup water and the opportunity for blowdown is limited, even low levels of impurities in the feed water rapidly become a critical concern. The condensate-polishing system recommended consists of a strong acid cation gel, NRW1140, to remove ammonia from condensate and a mixed bed, NRW3460, to complete the condensate-purification step. These resins can be regenerated onsite but non-regenerable resins are also available. These include the strong acid cation macroporous NRW160 and the mixed bed NRW3560. Keep in mind that the condensate flowrate and volume can be considerable. For example, a 500-MW power plant has to treat 4,000 m3/h (17,000 gpm) of condensate.
3. Turbo-blowers
Turbo-blowers are fans designed to keep carbon dioxide circulating through the reactor core to the heat exchangers. Each turbo-blower is driven by a steam pump using plant steam. Each steam turbine has its own condenser and the condensate must be treated with the same main condensate treatment resins described above.
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The coolant running through the reactor core is purified water and is given the term light water. Acting as both a heat transfer fluid and a moderator, it is heated to 290 320oC and maintained under a pressure of 150 bar (2,200 psi). The neutron flux rate can be controlled by varying the concentration of boric acid dissolved in this primary circuit water and by moving the control rods up and down. However, typical operation has the control rods almost completely withdrawn to maximize fuel burn-up. Large water pumps circulate the pressurized water through the steam generators, which function as heat exchangers. Certain PWR reactor designs such as the Candu system use heavy water. This is water highly enriched in the hydrogen isotope deuterium. Deuterium has a proton and a neutron in the nucleus whereas hydrogen has only a proton. Other than the moderator, the basics of the Candu reactor are the same as the PWR described herein. The PWR was originally designed in the United States by Westinghouses Bettis Atomic Power Laboratory for military ships. Westinghouse, Asea Brown Boveri-Combustion Engineering (ABB-CE), Framatome, Kraftwerk Union, Siemens, and Mitsubishi have typically built this type of reactor throughout the world. Babcock & Wilcox (B&W) built a PWR design but used vertical once-through steam generators rather than the U-tube design used by the rest of the suppliers. Industry consolidation has occurred so that Framatome-Areva-NP, Westinghouse, Mitsubishi and Toshiba are the key remaining manufacturers. Such reactors, especially the Westinghouse AP1000 and the Areva EPR designs, are expected to be widely used in the years to come and will constitute a major portion of the worlds nuclear power generation programs in the foreseeable future.
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These corrosion byproducts will become activated isotopes that release as crud bursts during cool down periods of outages. These buildups and releases can potentially damage fuel sheaths and contribute to fuel leaks and support Crud Induced Localized Corrosion (CILC). To further minimize colloidal and dissolved impurities, corrosion-resistant materials with special alloys, such as Zircaloy, Inconel and stainless steel are utilized. It must be noted, however, that stainless steel is sensitive to the presence of chloride in the water. Today, special corrosion-resistant stainless metals, such as Alloy690TT and Alloy 80Mod, are being used to replace current steam generators to minimize source term and extend unit life. Source term is latent radiation that builds up in the system and must be controlled. The pH of the primary water is typically maintained between 6.9 and 7.4 at 300C or coolant average temperature. This may change depending on materials of construction, water chemistry and system design. If necessary, it is adjusted up by adding lithium hydroxides. Lithium can be natural lithium, a mixture of two isotopes (approximately 7% 6Li+ and 93% 7Li+), or purified lithium (99.5% 7Li+). Natural lithium is notably less expensive but has the disadvantage of producing tritium by neutron capture of 6Li+. Purified 7Li+ is the principal lithium isotope used in a large majority of PWRs worldwide. The pH of the primary water must be maintained at the specified level and adjusted based on the water temperature. Reactor pH (temperature corrections of 0.2 to 2 units) is adjusted down by removing lithium. Boric acid is used to slow down neutrons. When a power plant starts up, the concentration of boric acid is typically 1,500 ppm as B. As the nuclear fuel activity decreases, the concentration is reduced progressively until low concentrations are reached by the end of the fuel life cycle. However, the plant may need to increase or decrease the boric acid concentration in order to adjust the power supply at a given moment. Natural boron is a combination of B11 and B10. B10 is a powerful neutron absorbent and changes into 7 + Li via a nuclear reaction known as radiolysis. Thus, the 7Li+ concentration is maintained within the circuit proportionally to the boric acid concentration.
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0.1 % of total active sites with chloride, or approximately 200 mg per kg of dry resin. Special attention should also be paid to the silica content in anionic resin, as silica found on the anionic resin is easily displaced by boric acid and can end up leaching into primary coolant.
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filters (0.1 m) to be used during outage activities, reducing the number of filters used, and, to a limited extent, assisting in the reduction of source term within the primary system. Currently there is a push to reduce nuclear waste because of lack of storage sites. Resins are now being used in more than one cycle. Originally the NRW5010 product was considered to be too fragile and not possible to be loaded on full service bed, but with the development of the stronger macroporous anion NRW5070, full power beds can be layered and used for possibly 2 cycles without concern of bead failure. Cleanup beds however may not be good candidates for multiple outages due to the high level and type of loading they encounter.
b. pH control
As mentioned earlier, pH is adjusted upward by adding lithium hydroxide and downward by removing lithium. Since B10 absorbs neutrons and changes into 7Li+ there may be an excessive increase in lithium in the circuit. This concentration is controlled by routing the mixed bed effluent (primarily Westinghouse systems) into a separate CVCS vessel loaded with strong acid cation resin NRW160 to remove excess lithium.
c. Outage Activity
When the reactor cavity coolant has reached the specified activity level the reactor coolant pumps (RCP) are stopped, steam generators isolated and the reactor head is lifted. From this point the cavity is flooded with water from the reactor or refueling water storage tank (RWST) and refueling begins. This creates a large pool where fuel bundles are manipulated under water. Some bundles are moved to a spent fuel pool through a refueling canal and continually remain submerged. Once the refueling has been completed, the reactor water is returned to the RWST or released to the radwaste stream for processing before discharge. The discharged water is termed primary effluent and includes primary circuit let down (water released from primary system to be replaced with water of a different boron concentration) and the various liquid waste streams originating from the radioactive sections of the power plant. These waters contain lithium and boron in addition to a large variety of radioactive isotopes. The effluents are filtered before being treated by ion exchangers. Usually the resin train consists of activated carbon, natural zeolite, a strong acid cation exchanger H+ form (NRW160, NRW1100, NRW1000), followed by mixed bed resins (NRW3240 or NRW3260). The strong acid cation exchanger removes lithium, cobalt, cesium etc. Fluoride and antimony are generally the difficult species to remove.
2. Deboration
The term deboration is related to ion exchange systems that will remove boron in a controlled manner. The deboration system removes residual boric acid remaining in the first part of the waste stream by ion exchange before passing to the radwaste processing system. The system may consist of an evaporator or a reverse osmosis system which produces a highly concentrated boron solution. The solution, according to its quality , is either recycled back to the primary circuit or directed to a treatment system for solid effluent. Permeate containing boron may be treated with nuclear grade strong base anion exchanger (NRW6000 or NRW7000). The Wolff Paper Apr 2012
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The capacity of the anion resin for boron will vary proportionally with the boric acid in the evaporator effluent or RO permeate. When the boron concentration increases, the anion resin operating capacity will increase. When boron is about 100 ppm, the operating capacity of the anion will be about 40 grams of boric acid per liter of resin.
Maintaining the clarity of both the reactor water and spent fuel pool water is crucial. Sediments are easily disturbed during fuel movement causing clarity to deteriorate and The Wolff Paper Apr 2012
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turbidity and radiation levels to increase. Use of the macroporous anion resins NRW5010 or NRW5070 assist in reducing turbidity and associated radioactivity when layered on top of the mixed bed resin. Additionally, if fuel bundles are moved from the fuel pool and transported to dry storage in special storage casks, the SFP demineralizer with an NRW5010 layer on the mixed bed removes fine particulates that collect on metal surfaces. This significantly reduces the task of decontaminating casks prior to moving them to storage. Figure 7: Activity buildup on anions used for RFO cleanup
Cleanup Bed Activity
4.5 4 3.5 3
uSv/h
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resins that are characterized by high total capacity and selectivity for influent cations such as sodium, and anions such as silica and chloride. This resin is also easily regenerated to a high level of conversion with minimal release of impurities. As a final polishing step before water enters the deionized water storage tank (DWST), a non-regenerable, high-purity mixed bed resin, such as UltraClean UCW9964 may be used. For a less separable mixed bed, UCW9966 can also be used. The makeup water quality will achieve 17.9 M, residual silica <2 ppb, residual sodium <0.02 ppb, residual TOC <1.5 ppb. When the final polishing UCW mixed bed is removed from service, it can be used as a regenerable resin elsewhere in the plant, but not returned to final polishing. When makeup water is from a surface water source, such as lakes, reservoirs or rivers, it may contain colloids, especially colloidal silica. Colloidal silica is difficult to remove by conventional filtration and ion exchange. Once it enters the steam generator, pressure and temperature convert into ionic silica which can form deposits on the steam generator and volatilize and deposit on the steam turbine. NRW5010 effectively removes colloidal silica from water and prevents it from entering the steam generator. If required, this targeted treatment step is best used in a stand-alone vessel following filtration pretreatment and regeneration with caustic.
6. Condensate Polishing
Treatment of condensate is essential for extending steam generator life. The goal is to remove iron and other corrosion elements in order to prevent deposits in the secondary circuit. In general, secondary chemistry is tightly controlled to maintain measurable iron levels below 0.8 ppb. Polishing resins are operated at high flow velocities up to 122 m/h (50 gpm/ft2). They are expected to remove ions such as sulfate to <0.2 ppb. This is especially true during condenser leaks. Proper selection of materials of construction is critical in minimizing corrosion in condensers. Special metals such as titanium are typically used, especially in the case of seawater cooling. Condenser manufacturing techniques are sometimes considered to be so complex that the risk of leakage has become theoretically negligible. This too has allowed many plants to minimize condensate polishing operation, however this represents risk. There are different ways to control secondary corrosion. First, secondary circuits are conditioned with hydrazine to remove trace oxygen. Second, condensate and steam generator water pH is maintained within a range of 8.8 to 10.5. This is done by the use of amines with the more common being ammonia, MPA (methoxy propylamine), and/or ETA (ethanolamine). The use of amines, especially ETA, can significantly reduce the formation and transport of iron-based corrosion products. Although favorable in reducing corrosion, this amine chemistry approach is suspected of negatively impacting condensate polishing resins by drawing foulants from the cation resin, fouling the anion resin and reducing kinetics. Theoretically ETA displaces (cleans) organo-sulfonates from the cation resin. These, in turn, accumulate on anion resin surfaces, thereby impairing kinetics. When anion resin becomes kinetically impaired, sulfate levels begin to increase in the steam generator. Therefore, anion resin kinetics must be monitored The Wolff Paper Apr 2012
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closely and when effectiveness decreases, the resins must be replaced. They should be replaced even if the ionic operating capacity has not been depleted completely. Plants using ETA-naturalizing amines may require a cation resin that has been specially manufactured and post treated to minimize foulants that degrade anion kinetics. Condensate polishing, which removes corrosion products and in-leakage, is accomplished primarily with deep mixed bed polishers and less frequently with precoat filters. Precoat filters are vessels that have several filter elements that are coated with a layer of powdered resins and are typically used where steam condenser water has a relatively low salinity and when the risk of leakage is considered small. When plants use fresh water for cooling, deep-bed condensate polishers are operated during startup or upset conditions. When plants cool with brackish or salt water, the deep beds are operated continuously. Care is required to ensure that the steam generator receives high-purity water containing 0.02 ppb of Na+, Cl-and SO4-, as these dissolved solids will concentrate in the steam generator as steam is produced. A small number of PWR plants regenerate their condensate-polishing resins. However, the level of purity required from the polishing resin is critical and regenerating this resin to achieve levels where sodium, chloride and sulfate do not leach is often difficult to attain. Special efforts must be taken to ensure proper separation of resins, minimize cross-contamination and minimize residual ions from regeneration remaining in the resins. These ions are Na+ on the strong acid cation and carboxylic groups that may form on the anion resin (See papers by Auerswald(7) and by Crone(8)). Polishing systems that are not regenerated will operate intermittently to extend the resin life. Once these condensate-polishing resins begin breaking on amine, the condensate-polishing resins must be replaced. A small number of condensate polishers do operate past the amine break, however, these plants have extremely high purity secondary systems and no cooling water leakage. The following Purolite deep-bed demineralizer resins are recommended for condensate polishing: 1. Non-regenerable polishers will use the strong acid macroporous cation exchanger NRW160, or gel NRW 1160, followed by the complimentary mixed bed NRW3560, or NRW3670. This system has a lead strong acid cation exchange resin which removes unwanted cations, corrosion products, ammonia, and amines. The H+ and OH- polishing mixed bed captures traces impurities and supports longer unit run times. This system is capable of operating the lead cation past the amine break and possibly to a sodium break as long as sodium on the cation (and anion) is low (<20mg/Kg). The mixed bed will operate past the amine break to a sodium break depending on operating conditions. The run time may be as long as 6 months. 2. Regenerable mixed bed polishing resins are the strong acid cation SGC650 and the strong base anion gel SGA550 or the macroporous anion PFA503OH. This mixed bed only system is also operated past the amine break to a sodium break. Conservative operations will operate only to the amine break.
3.
Non-regenerable mixed beds NRW3562 and NRW3672 The Wolff Paper Apr 2012
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4.
A non-regenerable mixed bed with 1:1 cation-to-anion ratio by volume addressing elevated amine chemistries is NRW3561 or 2:1 cation to anion by volume NRW3562. Items 3 and 4 above generally require the service cycle to stop at the ammonia break resulting in approximately 24 weeks service. If service continues beyond the ammonia break to a sodium break service time will be greater, approximately 6 weeks, but Na+ leakage to the hot well will also be higher.
Precoat filters (elements) are coated with a mixture of strong acid cation exchanger in H+ form (Microlite PrCH) or an ammonia-form exchanger (Microlite PrCN) and a strong base anion exchanger in OH- form (Microlite PrAOH). Precoat filters have a relatively limited capacity for removing soluble salts and thus become rapidly exhausted in the event of a condenser leak. However, powdered resins have an inherent advantage over bead resins in that they have less capital cost associated with precoat facilities than a regeneration system. Furthermore, filtration of corrosion products is more efficient with powdered resins than with bead resins. Precoat products are available premixed as mixed bed products, without fiber (Microlite MB) and with fiber (CG range). If precoats exhaust on pressure drop due to excess corrosion or crud, precoat with fiber may allow extended runs.
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break compared to plants using ETA. High cross-linked macroporous cations resins operated in the low sodium form will result in only a slight sodium excursion when the amine break is reached. However, sodium levels will drop back after a short time and be maintained at low levels until the sodium break occurs. Low-level sodium released from the lead cation will be removed by the downstream mixed bed (NRW3560 or NRW3670). The mixed bed following the cation bed may also be operated past an amine break to a sodium break. However, the sodium break is much sooner (typically occurring in a matter of weeks) compared to what is often experienced on the cation bed (several months). For plants with higher ammonia and amine levels, use of a mixed bed resin with a higher cation capacity may add additional bed life. NRW3562 has a 2:1 cation-to-anion ratio by volume, which provides approximately 4.2:1 equivalence cation-to-anion.
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As in the case of other reactors, regenerable ion exchange resins are typically used to produce demineralized water that meets the required quality of the plant, while non-regenerable, highly regenerated mixed beds are used for final polishing. These final polishing mixed bed resins are re-used in regenerable vessels after they are exhausted. Many nuclear units rely on service companies to supply makeup water in order to minimize the handling, storage and use of treatment chemicals and the production of chemical waste streams onsite.
2. Condensate Polishing
Condensate polishing is one of two methods to control purity of the BWR coolant after makeup polishing. This polishing is primarily accomplished by using precoat filters only on freshwater cooled units and deep bed ion exchange vessels for brackish and salt water cooled units. Units that rely on low-salinity cooling water commonly use precoat filters with powder resins (Microlite PrCH, PrAOH, MB and CG range). Although powdered resins have a disadvantage of rapid exhaustion in the event of a condenser leak, they do present the following advantages: Lower capital cost because regeneration facilities are not required Good filtration of corrosion products. For instance, the quantity of suspended matter in treated condensate is only a few ppb, and will generally be controlled under 0.8 ppb at the filter outlet, even when startup levels of inlet impurities (such as iron and copper) may be on the order of several ppm Powdered resins are used once and therefore are a minimal risk of deteriorating chemically, even at relatively high temperatures. It is thus possible to install the precoat filters after one of the low-pressure heat exchangers, to improve filtration. Consequently, powder-form resins are very widely used in BWR power plants in many countries
In brackish and saltwater-cooled systems, resins in bead form used in deep-bed polishers are primarily high-capacity gel form resins. However, macroporous exchange resins offer exceptional selectivity for cobalt-60 and iron compared to gel-type resins. Macroporous anion resins also have a greater affinity for particulate iron compared to gel resins. Mixed beds with an equivalent cation-to-anion ratio are preferred. Compared to the precoat polisher, deep-bed polishing systems ensure several hours of operation in the event of a leak in the cooling condenser. After the polishing step, condensate is sent directly to the reactor through the makeup line. Condensate polishing must both demineralize the stream and filter corrosion products, which are predominately iron. Note: No chemical condensate conditioning (amines) or reducing chemistry are used in BWR systems.
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5. Radwaste Treatment
Service water and wasted coolant from BWR operations must be treated to ensure that no radioactivity is released. Radioactivity originating from the plant is treated with mixed bed ion exchange resins to reduce activity to a level that is appropriate for release back to the environment. The mixed bed resin that is most appropriate for this application is NRW3240. If pretreatment clarification is not employed, the addition of a top layer of the macroporous anion NRW5010 or NRW5070 will significantly improve the removal of suspended colloids such as activated iron. Contract companies are often used to provide this waste-treatment service.
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In spite of its advantages, the LMFBR has gained limited interest due to shorter fuel life, higher operating cost and a plentiful supply of uranium fuel. Government regulations related to reprocessing Pu239, which is a weapons grade isotope, has limited the number of operating LMFBR to 20 units worldwide. To ensure better safety, the primary circuit transfers its heat to a secondary circuit, which also contains liquid sodium. The steam generator is part of the tertiary circuit. As you can see, an LMFBR offers limited ion exchange resin opportunities. The Wolff Paper Apr 2012
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Type of reactor
Graphite-gas reactors, PWR
Steam generator blowdown Primary coolant purification (CVCS, RCV) pH control Refueling Outage (RFO)
PWR PWR
PWR PWR
Radwaste
PWR-BWR
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resin but at a lower flowrate because of higher concentrations of dissolved solids in the generator. Additionally, this resin is designed to primarily remove sodium, metals, chlorides and sulfate. Because of the competition between sodium and ammonia, the resins are replaced when sodium leakage reaches a design level. Resin life can be as long as two years for very clean systems, but generally the life expectancy of resins in this service is between six weeks and six months. However, systems that are susceptible to condenser leaks may be changed every two weeks. There are a few plants that regenerate their steam generator blowdown resins. This is generally done for a lead cation resin. When the mixed bed exhausts both cation and mixed bed resins are replaced. Makeup resins are regenerable and these resins may last many years depending on influent water impurities. Service companies supply these resins under contract.
3. DECONTAMINATION CAPACITY
Resin capacity for radioactive isotopes is defined by the decontamination factor (DF), which is influent radioactivity divided by effluent radioactivity. This capacity depends on the nature and concentration of radioactivity isotopes being addressed and the density of functional groups on ion exchange resins used. Table 4 (below) presents relative affinities (ion selectivity) for cobalt and cesium, compared with lithium and hydrogen, for different degrees of cross-linking. Table 4: Ion selectivity for principal soluble cations on varying cross-linked cation resins DVB% Li H Co Cs 4% 0.9 1.0 2.65 2.0 8% 0.85 1.0 2.8 2.7 12% 0.81 1.0 2.9 3.2 16% 0.74 1.0 3.05 3.45
Table 4 shows that the affinity for cesium over H+ and Li+ ions increases with the cross-linking of the strong acid cation exchange resin, while the affinity for cobalt is slightly lower than cesium. Therefore, an exchange resin with high DVB (divinyl benzene) cross-linking has higher removal rates and therefore a longer cycle for removing cesium (NRW160) compared to the mixed beds containing this component (NRW3560 and NRW3540(Li/Li7). High cross-linked macroporous cation exchange resins have greater porosity, which allows higher molecular weight divalent ions greater access to the active sites within the bead. By contrast, highly cross-linked gel-type exchanger resins have a tighter matrix, and thus insufficient porosity. This results in lower operating capacity. However, certain higher cross-linked gel resins may have a greater capacity for smaller molecular weight ions, such as lithium and sodium, compared to comparable cross-linked macroporous resins.
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Table 5 presents results of tests carried out on coolant purification (primary circuit) containing lithium and boric acid. The tests compared a mixed bed resin with a gel type strong acid cation NRW3260 (normal cross-linkage) and a mixed bed resin with a macroporous type strong acid cation NRW3560 (high cross-linkage). The average influent was Co58 1.0E-3 Ci/cm, Cs137 3.0E-1 Ci/cm. Table 5: Decontamination Factors (DF)
Mixed bed with gel type SAC NRW3260 DF for DF for Cs 137 Co 58 3 1 61 32 127 Mixed bed with macroporous type SAC NRW3560 DF for DF for Cs 137 Co 58
Note: The DF are averaged over total treated volume. The DF increases when the concentration of activity increases in the solution. The DF will vary noticeably during the cycle and as the influent concentration changes.
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